Nationwide distribution of perfluoroalkyl ether carboxylic acids in Chinese diets: An emerging concern.

With the phase-out of perfluorooctanoic acid (PFOA) and its replacement by perfluoroalkyl ether carboxylic acids (PFECAs), there is a potential for increased exposure to various new PFECAs among the general population in China. While there are existing studies on dietary exposure to legacy perfluoroalkyl and polyfluoroalkyl substances (PFASs), research on dietary exposure to PFECAs, especially among the general Chinese populace, remains scarce. In the present study, we investigated the distribution of PFECAs in dietary sources from 33 cities across five major regions in China, along with the associated dietary intake. Analysis indicated that aquatic animal samples contained higher concentrations of legacy PFASs compared to those from terrestrial animals and plants. In contrast, PFECAs were found in higher concentrations in plant and terrestrial animal samples. Notably, hexafluoropropylene oxide dimer (HFPO-DA) was identified as the dominant compound in vegetables, cereals, pork, and mutton across the five regions, suggesting widespread dietary exposure. PFECAs constituted the majority of PFAS intake (57 %), with the estimated daily intake (EDI) of HFPO-DA ranging from 2.33 to 3.96 ng/kg bw/day, which corresponds to 0.78-1.32 times the reference dose (RfD) (3.0 ng/kg bw/day) set by the United States Environmental Protection Agency. Given the ubiquity of HFPO-DA and many other PFECAs in the nationwide diet of China, there is an urgent need for further research into these chemicals to establish relevant safety benchmarks or consumption advisory values for the diet.

Recovery of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) from water using foam fractionation with whey soy protein.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are persistent anthropogenic chemicals that are widely distributed in the environment and pose significant risks to human health. Foam fractionation has emerged as a promising method to recover PFOS/PFOA from water. However, PFOS/PFOA concentrations in wastewater are often inadequate to generate stable foams due to their high critical micelle concentrations and the addition of a cosurfactant is necessary. In this study, we developed whey soy protein (WSP) as a green frother and collector derived from soybean meal (SBM), which is an abundant and cost-effective agro-industrial residue. WSP exhibited excellent foaming properties across a wide pH range and demonstrated strong collection capabilities that enhanced the recovery of PFOS/PFOA. The mechanism underlying this collection ability was elucidated through various methods, revealing the involvement of electrostatic attraction, hydrophobic interaction, and hydrogen bonding. Furthermore, we designed a double plate internal to improve the enrichment of PFOS/PFOA by approximately 2.3 times while reducing water recovery. Under suitable conditions (WSP concentration: 300 mg/L, pH: 6.0, air flowrate: 300 mL/min), we achieved high recovery percentages of 94-98% and enrichment ratios of 7.5-12.8 for PFOS/PFOA concentrations ranging from 5 to 20 mg/L. This foam fractionation process holds great promise for the treatment of PFOS/PFOA and other per- and polyfluoroalkyl substances.

Environmental explanation of prostate cancer progression based on the comprehensive analysis of perfluorinated compounds.

Perfluorinated compounds (PFCs) are man-made chemicals used in the manufacture of many products with water and dirt repellent properties. Many diseases have been proved to be related to the exposure of PFCs, including breast fibroadenoma, hepatocellular carcinoma, breast cancer and leydig cell adenoma. However, whether the PFCs promote the progression of prostate cancer remains unclear. In this work, through comprehensive bioinformatics analysis, we discovered the correlation between the prostate cancer and five PFCs using Comparative Toxicogenomics Database (CTD), Gene Expression Omnibus (GEO) and The Cancer Genome Atlas (TCGA) databases. In addition, further analysis showed that several PFCs-related genes demonstrated strong prognostic value for prostate cancer patients. The survival analysis and receiver operating characteristic (ROC) curves revealed that PFCs-related genes based prognostic model held great predictive value for the prognosis of prostate cancer, which could potentially serve as an independent risk factor in the future. In vitro experiments verified the promotive role of perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) in the growth of prostate cancer cells. This study provided novel insights into understanding the role of PFCs in prostate cancer and brought attention to the environmental association with cancer risks and progression.

An analysis of the use of the relative source contribution term in derivation of drinking water standards using perfluorooctanoic acid as an example.

The relative source contribution (RSC) term has long been used by the US Environmental Protection Agency (USEPA) and state regulatory agencies in setting criteria in water. The RSC reflects the proportion of the total daily intake of a chemical that can be derived from water when all other sources of exposure (e.g., food, air) are considered. This term is applied by the USEPA and state regulatory agencies when deriving ambient water quality criteria, maximum contaminant level goals, and drinking water health advisories for noncarcinogenic and threshold carcinogenic compounds. The value assigned to the RSC term affects the calculated criteria directly, with the allowable concentration in water decreasing with a decreasing RSC. A default RSC value of 20%-applied by regulatory entities in the USA for more than 40 years-assumes that 80% of an individual's exposure to a chemical's reference dose is from nonwater sources. Although the RSC is a chemical-specific parameter, there are few instances where a value other than the default of 20% has been approved and used. In 2000, USEPA outlined the process for developing chemical-specific RSC values, yet primary use of the default RSC value has continued since then. This article reviews USEPA's methodology for deriving chemical-specific RSC values and provides a case example using perfluorooctanoic acid (PFOA) to explore how the USEPA and state regulatory agencies are applying USEPA's guidance. The case study highlights inconsistent derivation of the RSC term, rooted in limitations in the current methodology. We suggest additional clarification of and more thoughtful use of the available data that may not meet USEPA's current adequacy requirements. We also recommend that the USEPA discuss recommendations for using biomonitoring data to set RSCs. Integr Environ Assess Manag 2023;19:605-612. © 2022 SETAC.

Physical and barrier changes in gastrointestinal mucus induced by the permeation enhancer sodium 8-[(2-hydroxybenzoyl)amino]octanoate (SNAC).

Drug delivery systems (DDS) for oral delivery of peptide drugs contain excipients that facilitate and enhance absorption. However, little knowledge exists on how DDS excipients such as permeation enhancers interact with the gastrointestinal mucus barrier. This study aimed to investigate interactions of the permeation enhancer sodium 8-[(2-hydroxybenzoyl)amino]octanoate (SNAC) with ex vivo porcine intestinal mucus (PIM), ex vivo porcine gastric mucus (PGM), as well as with in vitro biosimilar mucus (BM) by profiling their physical and barrier properties upon exposure to SNAC. Bulk mucus permeability studies using the peptides cyclosporine A and vancomycin, ovalbumin as a model protein, as well as fluorescein-isothiocyanate dextrans (FDs) of different molecular weights and different surface charges were conducted in parallel to mucus retention force studies using a texture analyzer, rheological studies, cryo-scanning electron microscopy (cryo-SEM), and single particle tracking of fluorescence-labelled nanoparticles to investigate the effects of the SNAC-mucus interaction. The exposure of SNAC to PIM increased the mucus retention force, storage modulus, viscosity, increased nanoparticle confinement within PIM as well as decreased the permeation of cyclosporine A and ovalbumin through PIM. Surprisingly, the viscosity of PGM and the permeation of cyclosporine A and ovalbumin through PGM was unaffected by the presence of SNAC, thus the effect of SNAC depended on the regional site that mucus was collected from. In the absence of SNAC, the permeation of different molecular weight and differently charged FDs through PIM was comparable to that through BM. However, while bulk permeation of neither of the FDs through PIM was affected by SNAC, the presence of SNAC decreased the permeation of FD4 and increased the permeation of FD150 kDa through BM. Additionally, and in contrast to observations in PIM, nanoparticle confinement within BM remained unaffected by the presence of SNAC. In conclusion, the present study showed that SNAC altered the physical and barrier properties of PIM, but not of PGM. The effects of SNAC in PIM were not observed in the BM in vitro model. Altogether, the study highlights the need for further understanding how permeation enhancers influence the mucus barrier and illustrates that the selected mucus model for such studies should be chosen with care.

Enhanced toxicity effects of iron particles together with PFOA in drinking water.

Iron particles present in drinking water distribution systems (DWDSs) could cause discoloration, while organic pollutants in DWDSs, such as perfluorooctanoic acid (PFOA), could be enriched by iron particles. However, little is known about the enhanced effects of PFOA and iron particles in DWDSs. To fill in these knowledge gaps, herein, iron-PFOA (FEP) particles were generated using residual chlorine as an oxidant in drinking water conditions and then separated into different sizes (ranging from small to large: FEP-S, FEP-M ，and FEP-L). FEP-S harbored the greatest cytotoxicity among the sizes. Interestingly, our data revealed that the PFOA released from FEP particles transformed into PFOS (perfluorooctane sulfonate) upon digestion in the gastrointestinal environment (GI), and FEP-L bored the strongest transformation, showing a toxicity profile that was distinct from that of FEP-S. Furthermore, mechanistic studies revealed that FEP per se should be accountable for the conversion of PFOA to PFOS dependent on the generation of hydroxyl radicals (·OH) in GI, and that FEP-L revealed the greatest production of ·OH. Collectively, these results showed how iron particles and PFOA could result in enhanced toxicity effects in drinking water: (i) PFOA could increase the toxicity of iron particles by reducing particle size and inducing higher generation of ·OH; (ii) iron particles could induce the transformation of PFOA into more toxic PFOS through digestion.

Ion exchange solid phase microextraction coupled to liquid chromatography/laminar flow tandem mass spectrometry for the determination of perfluoroalkyl substances in water samples.

Per- and polyfluoroalkyl substances (PFAS) are toxic and bioaccumulative compounds that are persistent in the environment due to their water and heat resistant properties. These compounds have been demonstrated to be ubiquitous in the environment, being found in water, soil, air and various biological matrices. The determination of PFAS at ultra-trace levels is thus critical to assess the extent of contamination in a particular matrix. In this work, solid phase microextraction (SPME) was evaluated as a pre-concentration technique to aid the quantitation of this class of pollutants below the EPA established advisory limits in drinking water at parts-per-trillion levels. Four model PFAS with varying physicochemical properties, namely hexafluoropropylene oxide dimer acid (GenX), perfluoro-1- butanesulfonate (PFBS), perfluoro-n-octanoic acid (PFOA) and perfluoro-1-octanesulfonate (PFOS) were studied as a proof of concept. Analysis was performed with the use of ultra-high pressure liquid chromatography-laminar flow tandem mass spectrometry (UHPLC-MS/MS). This study proposes the use of hydrophilic-lipophilic balance-weak anion-exchange/polyacrylonitrile (HLB-WAX/PAN) as a SPME coating, ideal for all model analytes. A sample volume of 1.5 mL was used for analysis, the optimized protocol including 20 min extraction, 20 min desorption and 6 min LC/MS analysis. This method achieved LOQs of 2.5 ng L- 1 (PFOS) and 1 ng L - 1 (GenX, PFBS and PFOA) with satisfactory precision and accuracy values evaluated over a period of 5 days.

An effective chromatographic fingerprinting workflow based on comprehensive two-dimensional gas chromatography - Mass spectrometry to establish volatiles patterns discriminative of spoiled hazelnuts (Corylus avellana L.).

The volatile fraction of hazelnuts encrypts information about: cultivar/geographical origin, post-harvest treatments, oxidative stability and sensory quality. However, sensory features could be buried under other dominant chemical signatures posing challenges to an effective classification based on pleasant/unpleasant notes. Here a novel workflow that combines Untargeted and Targeted (UT) fingerprinting on comprehensive two-dimensional gas-chromatographic patterns is developed to discriminate spoiled hazelnuts from those of acceptable quality. By flash-profiling, six hazelnut classes are defined: Mould, Mould-rancid-solvent, Rancid, Rancid-stale, Rancid-solvent, and Uncoded KO. Chromatographic fingerprinting on composite 2D chromatograms from samples belonging to the same class (i.e., composite class-images) enabled effective selection of chemical markers: (a) octanoic acid that guides the sensory classification being positively correlated to mould; (b) Æ´-nonalactone, Æ´-hexalactone, acetone, and 1-nonanol that are decisive to classify OK and rancid samples; (c) heptanoic and hexanoic acids and Æ´-octalactone present in high relative abundance in rancid-solvent and rancid-stale samples.

Environmental applications of a biodegradable cysteine-based surfactant.

An improved method has been developed for the efficient synthesis of octanoyl-cysteine in single-chain form (N-octanoyl-cys) which operates as a surfactant over a wide pH range, is easily decomposed into natural products and has a high product yield. The compound offers an environmentally acceptable agent for the adsorption of a range of heavy metals from contaminated waters/soils, and it could also be used in general household detergents or personnel-cleaner formulations, and even in toothpastes. The surfactant was used as a co-surfactant for flotation of perfluorooctanoic acid (PFOA), a per/poly-fluoroalkyl substance (PFAS). The new surfactant produced significant foaming and removed 70% of the PFOA after 30min of foam fractionation. The compound is also potentially useful in facilitating the release of PFAS compounds; these are negatively charged and often bound to charged particles in sand, clay, and humic-acid-coated materials and microorganisms via bridging multivalent ions, such as Ca2+, Mg2+, Al3+ and Fe3+, as well as a range of other heavy-metal ions present in soil to varying degrees. In soils (and also in contaminated water), the common chelating agent EDTA is often used to encapsulate these ions (e.g. Ca2+, the dominant ion in soil) at moderately high pH to aid in the release of the bound PFAS compounds. However, it would be more environmentally acceptable to use this new biodegradable surfactant, which could combine chelation with foam-fractionation separation of surface-active (e.g. PFAS) components in soils.

Investigating isomers/enantiomers of perfluorooctanoic acid in river water by gas chromatography-mass spectrometry with chiral derivatization.

Perfluorooctanoic acid (PFOA) in environmental media contains numerous isomers/enantiomers because of the PFOA manufacturing process and biological degradation of PFOA precursors. Few methods for analyzing PFOA enantiomers have been described. A simple derivatization method using (S)-1-phenethyl chloride that was developed to allow PFOA isomers/enantiomers to be separated by gas chromatography and analyzed by electron-capture negative ionization mass spectrometry is described here. PFOA standards were analyzed, and enantiomers of the chiral isomers perfluoro-3-methyl-heptanoic acid, perfluoro-4-methyl-heptanoic acid, and perfluoro-3,5-dimethyl-hexanoic acid were separated using an HP-5MS column. Linear PFOA and perfluoro-6-methyl-heptanoic acid were chromatographically separated from these enantiomers. The linear ranges (giving correlation coefficients r > 0.997) of the calibration curves for the isomers were 0.010-3.00 ng/mL. PFOA isomer/enantiomer concentrations in river water were determined using the method. The method separated the enantiomers of perfluoro-3-methyl-heptanoic acid and perfluoro-4-methyl-heptanoic acid, the isomers of perfluoro-6-methyl-heptanoic acid, and linear PFOA in river water. No significant differences were found between the PFOA enantiomer/isomer compositions of the sample and technical PFOA. Enantiomer ratios can provide information about the sources and transport of pollutant isomers/enantiomers in the environment. Enantiomeric separation requires effective separation techniques. Our method achieved chiral separation using a non-chiral GC column that is often used in general analytical laboratories. The method could be used to investigate the sources and fates of PFOA and the isomers/enantiomers of other potentially toxic persistent pollutants in the environment and the risks posed to humans.

Sociodemographic and behavioral determinants of serum concentrations of per- and polyfluoroalkyl substances in a community highly exposed to aqueous film-forming foam contaminants in drinking water.

BACKGROUND: Per- and polyfluoroalkyl substances (PFAS) are a chemical class widely used in industrial and commercial applications because of their unique physical and chemical properties. Between 2013 and 2016 PFAS were detected in public water systems and private wells in El Paso County, Colorado. The contamination was likely due to aqueous film forming foams used at a nearby Air Force base. OBJECTIVE: To cross-sectionally describe the serum concentrations of PFAS in a highly exposed community, estimate associations with drinking water source, and explore potential demographic and behavioral predictors. METHODS: In June 2018, serum PFAS concentrations were quantified and questionnaires administered in 213 non-smoking adult (ages 19-93) participants residing in three affected water districts. Twenty PFAS were quantified and those detected in >50% of participants were analyzed: perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA) and perfluoroheptane sulfonate (PFHpS). Unadjusted associations were estimated between serum PFAS concentrations and several predictors, including water consumption, demographics, personal behaviors and employment. A multiple linear regression model estimated adjusted associations with smoking history. RESULTS: Study participants' median PFHxS serum concentration (14.8 ng/mL) was approximately 12 times as high as the U.S. national average. Median serum concentrations for PFOS, PFOA, PFNA and PFHpS were 9.7 ng/mL, 3.0 ng/mL, 0.4 ng/mL and 0.2 ng/mL, respectively. Determinants of PFHxS serum concentrations were water district of residence, frequency of bottled water consumption, age, race/ethnicity, and smoking history. Determinants of serum concentrations for the other four PFAS evaluated included: water district of residence, bottled water consumption, age, sex, race/ethnicity, smoking history, and firefighter or military employment. CONCLUSIONS: Determinants of serum concentrations for multiple PFAS, including PFHxS, included water district of residence and frequency of bottled water consumption. Participants' dominant PFAS exposure route was likely consumption of PFAS-contaminated water, but certain demographic and behavioral characteristics also predicted serum concentrations.

Exposure assessment to parabens, bisphenol A and perfluoroalkyl compounds in children, women and men by hair analysis.

Population is continuously exposed to endocrine disrupting compounds present in everyday products such as parabens, bisphenol A (BPA), and perfluoroalkyl compounds (PFCs). The aims of this study were, first, to evaluate human exposure to three parabens (methylparaben (MeP), ethylparaben (EtP) and propylparaben (PrP)), BPA and six PFCs (perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS)) through the analysis of hair samples from children, women and men and, then, to evaluate possible relationships between pollutant concentration in hair and age, gender, smoking and dyeing habits or hair colour. Hair samples were collected from 42 volunteers from Seville (Spain) (10 children, 16 women and 16 men). Six of the monitored pollutants (MeP, EtP, PrP, BPA, PFHpA and PFOS) were detected in at least 76% of the samples analysed. The highest concentrations and frequency of detection (100% of the samples) corresponded to MeP and PrP (up to 14,187 and 9009 ng/g, respectively). BPA was found in 83% of the samples at concentrations in the range from 24 to 1427 ng/g whereas PFCs were detected at concentrations in the range from 0.6 to 15.5 ng/g, being PFHpA and PFOS the ones most frequently detected (86% and 76%, respectively). Concentrations of BPA and parabens in adults were statistically higher than those in children. The results of this study reveal the suitability of hair for biomonitoring endocrine disrupting compounds of high concern (PFCs, parabens and BPA) to which population is internally or/and externally but continuously exposed.

Removal of pharmaceutical compounds, artificial sweeteners, and perfluoroalkyl substances from water using a passive treatment system containing zero-valent iron and biochar.

Emerging contaminants are widely detected and persistent in environmental waters. Advanced oxidation processes are among the most effective methods for removing emerging contaminants from water; however, high energy consumption greatly increases the operating costs and limits large-scale applications. In this study, a passive treatment system consisting of four columns packed with mixtures of silica sand, zero-valent iron (ZVI), biochar (BC), and a mixture of (ZVI + BC) were evaluated for simultaneous removal of eight pharmaceuticals, four artificial sweeteners, and two perfluoroalkyl substances (PFASs) from water. Overall, the passive treatment system was more effective for removing target pharmaceuticals (almost complete removal) than artificial sweeteners and PFASs (partial removal). Columns ZVI, BC, and (ZVI + BC) exhibited similarly effective removal (>97%) of target pharmaceuticals, including carbamazepine, caffeine, sulfamethoxazole, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, ibuprofen, gemfibrozil, and naproxen, from ~9 to <0.25 µg L-1; pharmaceuticals were more rapidly removed by Columns ZVI and (ZVI + BC) than Column BC, except for ibuprofen. Column ZVI was more effective for removing artificial sweeteners acesulfame-K and sucralose than Columns BC and (ZVI + BC); however, BC exhibited relatively greater removal of saccharin than ZVI and (ZVI + BC). Acesulfame-K and saccharin (~110 µg L-1) were partially removed in the treatment columns. Cyclamate was not removed in any of the columns. However, >76% of input sucralose (~110 µg L-1) was removed in the three treatment columns. Reactive medium BC alone was more effective for removing target PFASs than ZVI and (ZVI + BC). Input perfluorooctanoic acid (PFOA) (~45 µg L-1) was partially removed in the columns containing BC but not ZVI alone. Between 10 and 80% of input perfluorooctane sulfonic acid (PFOS) (24 ̶ 90 µg L-1) was removed in Column ZVI; greater removals (57 ̶ 99%) were observed in Columns BC and (ZVI + BC).

Perfluoroalkyl substances are inversely associated with coronary heart disease in adults with diabetes.

AIMS: Perfluoroalkyl substances (PFAS) are environmentally and biologically persistent synthetic environmental contaminants linked to adverse health outcomes. Though null to modest inverse relationships between PFAS and coronary heart disease (CHD) have been reported, studies regarding relationships in high risk populations such as those with diabetes are sparse. We investigated the relationship of PFAS with CHD in persons with diabetes. METHODS: Data on 5270 adults, aged ≥20 years, with diabetes were obtained from the C8 Health Project. Four PFAS were investigated separately: perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), and perfluorononanoic acid (PFNA). RESULTS: In logistic regression analyses adjusting for age, sex, diabetes duration, BMI, smoking, lipids, WBC, CRP, eGFR, uric acid, hemoglobin and iron, all PFAS were inversely associated with CHD, ORs (95% CIs): PFHxS; 0.72 (0.65-0.79), PFOA; 0.90 (0.81-0.96), PFOS; 0.90 (0.81-0.99), PFNA; 0.88 (0.76-1.02). Stratification by chronic kidney disease status revealed similar inverse relationships for those with and without chronic kidney disease. CONCLUSIONS: In this cross-sectional study of over 5000 adults with diabetes, PFAS showed inverse associations with CHD. These findings may, if confirmed in future studies, provide new physiologic understanding of CHD prevention strategies.

Olfactory impact of esters on rose essential oil floral alcohol aroma expression in model solution.

This study focused on the impact of esters on the perception of floral aroma in rose essential oil. Various aromatic reconstitutions were prepared, consisting of 10 alcohols and 9 esters, all the concentrations found in rose essential oil. Sensory analysis by the triangular tests revealed the interesting behavior of certain compounds among the 9 esters following their addition or omission. The results tend to highlight the important role of ethyl octanoate, ethyl tetradecanoate, citronellyl acetate, geranyl acetate, and 2-phenethyl acetate of esters in rose essential oil. The "olfactory threshold" (OT) of the 5 esters, the floral reconstitution and the mixtures of ester and floral reconstitution were evaluated in alkanes solution. Through the Feller's additive model analysis, it was found that the presence of ethyl octanoate, ethyl tetradecanoate, and citronellyl acetate led to a significant in decrease the OT of the mixtures, whereas geranyl acetate raised the OT. The floral reconstitution in alkanes solution was supplemented with the 5 esters at high, medium, and low concentration, then analyzed by quantitative descriptive analysis. It was revealed that ethyl octanoate, ethyl tetradecanoate, and citronellyl acetate adding overall aroma, and geranyl acetate masking the overall aroma perception in a model floral mixture. Sensory profiles highlighted changes in the perception of aroma nuances in the presence of the 5 esters, with specific perceptive interactions, and reported on the graph based on two parameters [σ = f(τ)]. This paper provided a reference for the flavourists.

Sorption of PFOA onto different laboratory materials: Filter membranes and centrifuge tubes.

Measurement and reporting of concentrations of contaminants of emerging concern such as per- and polyfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA), is an integral part of most investigations. Occurrence of sorption losses of PFAS analytes onto particular laboratory-ware (e.g. glass containers) has been suggested in the published literature but has not been investigated in detail. We examined sorption losses from aqueous PFOA solutions in contact with different commonly-used materials in filter units and centrifuge tubes (glass and plastics). Sorption of PFOA onto different filter membrane types ranged from 21-79% indicating that filtration can introduce a major source of error in PFOA analysis; pre-treatment of filter membranes with phosphate or methanol solutions did not improve PFOA recovery. Substantial adsorption of PFOA was also observed on tubes made from polypropylene (PP), polystyrene (PS), polycarbonate (PC), and glass where losses observed were between 32-45%, 27-35%, 16-31% and 14-24%, respectively. Contrary to suggestions in the literature, our results indicated that the greatest sorption losses for PFOA occurred on PP, whereas losses on glass tubes were much lower. Variations in ionic strength and pH did not greatly influence PFOA recovery. When PFOA concentrations were increased, the percent recovery of PFOA increased, indicating that binding sites on tube-walls were saturable. This study draws attention towards analytical bias that can occur due to sorption losses during routine procedures, and highlights the importance of testing the suitability of chosen laboratory-ware for specific PFAS analytes of interest prior to experimental use.

Distribution, partitioning and inhalation exposure of perfluoroalkyl acids (PFAAs) in urban and rural air near Lake Chaohu, China.

To investigate the distribution, partitioning, and inhalation exposure risks of perfluoroalkyl acids (PFAAs), gaseous and particulate samples were collected monthly between September 2013 and September 2015 in urban and rural areas near Lake Chaohu. Twelve PFAAs were determined by liquid chromatography-mass spectrometry. The mean concentrations of PFAAs in the gaseous phase and the particulate phase were 40.31 ±â€¯31.47 pg/m3 and 63.26 ±â€¯41.87 pg/m3, respectively. Perfluorobutanoic acid (PFBA) was the predominant contaminant in the gaseous phase (32.56% ±â€¯9.28%), while perfluorooctanoic acid (PFOA) was the main contaminant in the particulate phase (33.21% ±â€¯18.69%). The ratios of gaseous to particulate distribution ranged from 0.01 to 16.75. The gaseous-particulate partitioning coefficients, ranging from 0.01 to 23.41 ±â€¯10-2 m3/µg, were significantly correlated with PM10 concentrations and meteorological conditions, such as temperature and air pressure. The inhalation exposures of PFOA and PFOS were 1.94-60.2 pg/(kg·d) and 0.30-4.22 pg/(kg·d), respectively. The carcinogenic risk of PFOA for urban males was the highest and that for rural females was the lowest; the risks were lower than the acceptable level (10-6) defined by the US Environmental Protection Agency (USEPA). The non-carcinogenic risks of PFOA and PFOS were far below one.

Temperature-dependent Henry's Law constants of 4-alkyl branched-chain fatty acids and 3-methylindole in an oil-air matrix and analysis of volatiles in lamb fat using selected ion flow tube mass spectrometry.

RATIONALE: 4-Alkyl branched-chain fatty acids and 3-methylindole are characteristic flavor compounds associated with sheep meat. Determining their partitioning behavior between the gas and condensed phase and ultimately developing a correlation between the compound's headspace concentration and sensory descriptive grouping are important for high-throughput characterization and grading classification. METHODS: The headspace concentrations of 3-methylindole, 4-methyloctanoic acid, 4-ethyl-octanoic acid, and 4-methylnonanoic acid above corn-oil-based standard solutions and lamb fat samples were measured using selected ion flow tube-mass spectrometry (SIFT-MS). The standard solutions were equilibrated at 80, 100, 110 and 125°C while the fat samples were equilibrated at 125°C. Statistical evaluation, linear and polynomial regression analyses were performed to establish the compound-specific and temperature-dependent Henry's Law constants, enthalpy (ΔH) and entropy (ΔS) of phase changes. RESULTS: The Henry's Law constants (kHcp ) were calculated from the regression analysis with a high degree of confidence (p < 0.05) and linearity (r2  > 0.99). The kHcp increased with increase in equilibrium temperature. The empirical calculation of ΔH and ΔS at different temperatures confirmed the temperature-dependence of the Henry's Law constants. The headspace concentrations of the lamb-flavor compounds were determined above actual lamb fat samples and the corresponding condensed-phase concentrations were successfully derived. CONCLUSIONS: The temperature-dependent Henry's Law constants, ΔH, and ΔS of phase changes for 3-methylindole, 4-methyloctanoic acid, 4-ethyloctanoic acid, and 4-methylnonanoic acid in an air-oil matrix were empirically derived. The effectiveness of SIFT-MS for the direct, real-time, and rapid determination of key flavor compounds in lamb fat samples was established.

Gastric Activity and Gut Peptides in Patients With Functional Dyspepsia: Postprandial Distress Syndrome Versus Epigastric Pain Syndrome.

GOALS: The goals of the study were to investigate in both postprandial distress syndrome (PDS) and epigastric pain syndrome (EPS) the gastric electrical activity and the gastric emptying (GE) time together with the circulating concentrations of motilin, somatostatin, corticotrophin-releasing factor, and neurotensin, and to establish whether the genetic variability in the neurotensin system genes differs between these 2 categories of functional dyspepsia (FD). BACKGROUND: The current FD classification is based on symptoms and it has been proven not to be completely satisfying because of a high degree of symptom overlap between subgroups. STUDY: Gastric electrical activity was evaluated by cutaneous electrogastrography: the GE time by C-octanoic acid breast test. Circulating concentrations of gut peptides were measured by a radioimmunoassay. NTS 479 A/G and NTSR1 rs6090453 SNPs were evaluated by PCR and endonuclease digestion. RESULTS: Fifty-four FD patients (50 female/4 male) were studied. Using a symptom questionnaire, 42 patients were classified as PDS and 12 as EPS, although an overlap between the symptom profiles of the 2 subgroups was recorded. The electrogastrographic parameters (the postprandial instability coefficient of dominant frequency, the dominant power, and the power ratio) were significantly different between the subgroups, whereas the GE time did not differ significantly. In addition, EPS was characterized by a different gut peptide profile compared with PDS. Finally, neurotensin polymorphism was shown to be associated with neurotensin levels. This evidence deserves further studies in consideration of an analgesic role of neurotensin. CONCLUSIONS: Analysis of gut peptide profiles could represent an interesting tool to enhance FD diagnosis and overcome limitations due to a distinction based solely on symptoms.

Natural variability in acyl moieties of sugar esters produced by certain tobacco and other Solanaceae species.

A unique feature of glandular trichomes of plants in the botanical family Solanaceae is that they produce sugar esters (SE), chemicals that have been shown to possess insecticidal, antifungal, and antibacterial properties. Sugar esters of tobacco (Nicotiana tabacum) provide pest resistance, and are important flavor precursors in oriental tobacco cultivars. Acyl moieties of SEs in Nicotiana spp., petunia, and tomato are shown to vary with respect to carbon length and isomer structure (2-12 carbon chain length; anteiso-, iso-, and straight-chain). Sugar esters and their acyl groups could serve as a model to explore the basis of phenotypic diversity and adaptation to natural and agricultural environments. However, information on the diversity of acyl composition among species, cultivars, and accessions is lacking. Herein, described is the analysis of SE acyl groups found in 21 accessions of Nicotiana obtusifolia (desert tobacco), six of Nicotiana occidentalis subsp. hesperis, three of Nicotiana alata, two of N. occidentalis, four modern tobacco cultivars, five petunia hybrids, and one accession each of a primitive potato (Solanum berthaultii) and tomato (Solanum pennellii). A total of 20 different acyl groups was observed that were represented differently among cultivars, species, and accessions. In Nicotiana species, acetate and iso- and anteiso-branched acids prevailed. Straight-chain groups (2-8 carbons) were prominent in petunias, while octanoic acid was prominent in N. alata and N. × sanderae. Two unexpected acyl groups, 8-methyl nonanoate and decanoate were found in N. occidentalis subsp. hesperis. Longer chain groups were found in the petunia, tomato, and potato species studied.